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Up till now I have been using cookies to pass information from page to page. How can I use sessions to, after using a function to confirm a users identity, would hold their username and password in the session to make available to other pages?

Pretty simple, try this manual: www.php.net/session
In the login page, you would session_register the username+password if they're correct, then on follow-up pages, call session_start as well as checking the variables (username+passowrd) are registered before (so they're actually passed through login page)